Composite membrane including ion-conductive polymer layer and gas blocking inorganic particles, method of preparing the composite membrane, and lithium air battery including the composite membrane

ABSTRACT

A composite membrane includes an ion-conductive polymer layer; and a plurality of gas blocking inorganic particles non-continuously aligned on the ion-conductive polymer layer, wherein the composite membrane has a radius of curvature of about 10 millimeters or less.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority to U.S. patent application Ser. No.15/646,239 filed Jul. 11, 2017, and Korean Patent Application No.10-2016-0098451, filed on Aug. 2, 2016 in the Korean IntellectualProperty Office, and all the benefits accruing therefrom under 35 U.S.C.§§ 119, 120, the contents of which are incorporated herein by referencein their entirety.

BACKGROUND 1. Field

The present disclosure relates to a composite membrane, a method ofpreparing the composite membrane, and a lithium air battery includingthe composite membrane.

2. Description of the Related Art

A lithium air battery includes an anode, a cathode that uses oxygen inthe air as a cathode active material and includes a catalyst foroxidizing and reducing oxygen, and a lithium ion-conductive mediumbetween the cathode and the anode.

Lithium air batteries have a theoretical energy density of about 3,000watt hours per kilogram (Wh/kg) or greater, which is remarkably higherthan that of lithium ion batteries. Furthermore, lithium air batteriesare more environmentally friendly and safer in use than lithium ionbatteries. To improve the cell performance of such a lithium airbattery, there is a need for an improved separator with the ability toeffectively block moisture and gas while also enabling lithium ions topass through.

SUMMARY

Provided is a composite membrane and a method of preparing the compositemembrane.

Provided is a lithium air battery with improved cell performanceincluding the composite membrane.

Additional aspects will be set forth in part in the description whichfollows and, in part, will be apparent from the description, or may belearned by practice of the presented embodiments.

According to an aspect, a composite membrane includes: an ion-conductivepolymer layer; and a plurality of gas blocking inorganic particlesnon-continuously disposed on the ion-conductive polymer layer, whereinthe composite membrane has a radius of curvature of about 10 millimetersor less.

According to an aspect, a method of preparing the composite membraneincludes: preparing a composition including the ion-conductive polymerand an organic solvent; disposing the composition onto a porous base;applying the plurality of gas blocking inorganic particles to thecomposition; and drying the gas blocking inorganic particles and thecomposition to prepare the composite membrane.

According to an aspect of another example embodiment, a lithium airbattery includes an anode, a cathode, and the composite membrane betweenthe anode and the cathode.

According to an aspect, a battery assembly includes an electrolyte; alithium metal or a lithium metal alloy; and the composite membrane.

BRIEF DESCRIPTION OF THE DRAWINGS

These and/or other aspects will become apparent and more readilyappreciated from the following description of the example embodiments,taken in conjunction with the accompanying drawings in which:

FIG. 1A is a schematic perspective view of an embodiment of a compositemembrane;

FIG. 1B is a schematic perspective view of another embodiment of acomposite membrane;

FIG. 2 is a schematic illustration for explaining an embodiment of amethod of preparing a composite membrane;

FIG. 3A is a schematic cross-sectional view illustrating a structure ofan embodiment of a lithium air battery;

FIG. 3B is a schematic view illustrating a structure of an embodiment oflithium air battery, the lithium air battery including an embodiment ofthe composite membrane;

FIG. 3C is a perspective view illustrating a radius of curvature of acomposite membrane;

FIG. 4A is a schematic cross-sectional view illustrating a structure ofa composite membrane of Example 2;

FIG. 4B is a schematic cross-sectional view illustrating a structure ofa membrane of Comparative Example 4 as a gas blocking membrane;

FIGS. 5A and 5B are scanning electron microscopic (SEM) images of topand bottom surfaces, respectively, of the composite membrane of Example2;

FIGS. 5C and 5D are SEM images of top and bottom surfaces of thecomposite membrane of Comparative Example 4, respectively;

FIG. 6A is a graph of resistance (ohms) versus time (hours; h)illustrating the resistance characteristics of the battery assemblies ofExamples 4 and 5 and Comparative Example 5; and

FIG. 6B is a graph of resistance (ohms) versus time (h) illustrating theresistance characteristics of the battery assemblies of Example 6 andComparative Example 6.

DETAILED DESCRIPTION

Reference will now be made in detail to an embodiment of a compositemembrane, a method of preparing the composite membrane, and a lithiumair battery including the composite membrane, examples of which areillustrated in the accompanying drawings, wherein like referencenumerals refer to like elements throughout. In this regard, the presentembodiments may have different forms and should not be construed asbeing limited to the descriptions set forth herein. Accordingly, theembodiments are merely described below, by referring to the figures, toexplain aspects. As used herein, the term “and/or” includes any and allcombinations of one or more of the associated listed items. “Or” means“and/or.” Expressions such as “at least one of,” when preceding a listof elements, modify the entire list of elements and do not modify theindividual elements of the list.

The terminology used herein is for the purpose of describing particularembodiments only and is not intended to be limiting. As used herein, thesingular forms “a,” “an,” and “the” are intended to include the pluralforms, including “at least one,” unless the content clearly indicatesotherwise. “At least one” is not to be construed as limiting “a” or“an.” It will be further understood that the terms “comprises” and/or“comprising,” or “includes” and/or “including” when used in thisspecification, specify the presence of stated features, regions,integers, steps, operations, elements, and/or components, but do notpreclude the presence or addition of one or more other features,regions, integers, steps, operations, elements, components, and/orgroups thereof.

It will be understood that, although the terms “first,” “second,”“third,” etc. may be used herein to describe various elements,components, regions, layers, and/or sections, these elements,components, regions, layers, and/or sections should not be limited bythese terms. These terms are only used to distinguish one element,component, region, layer, or section from another element, component,region, layer, or section. Thus, “a first element,” “component,”“region,” “layer,” or “section” discussed below could be termed a secondelement, component, region, layer, or section without departing from theteachings herein.

Furthermore, relative terms, such as “lower” or “bottom” and “upper” or“top,” may be used herein to describe one element's relationship toanother element as illustrated in the Figures. It will be understoodthat relative terms are intended to encompass different orientations ofthe device in addition to the orientation depicted in the Figures. Forexample, if the device in one of the figures is turned over, elementsdescribed as being on the “lower” side of other elements would then beoriented on “upper” sides of the other elements. The exemplary term“lower,” can therefore, encompasses both an orientation of “lower” and“upper,” depending on the particular orientation of the figure.Similarly, if the device in one of the figures is turned over, elementsdescribed as “below” or “beneath” other elements would then be oriented“above” the other elements. The exemplary terms “below” or “beneath”can, therefore, encompass both an orientation of above and below.

It will be understood that when an element is referred to as being “on”another element, it can be directly on the other element or interveningelements may be present therebetween. In contrast, when an element isreferred to as being “directly on” another element, there are nointervening elements present.

“About” or “approximately” as used herein is inclusive of the statedvalue and means within an acceptable range of deviation for theparticular value as determined by one of ordinary skill in the art,considering the measurement in question and the error associated withmeasurement of the particular quantity (i.e., the limitations of themeasurement system). For example, “about” can mean within one or morestandard deviations, or within ±30%, 20%, 10%, or 5% of the statedvalue.

Unless otherwise defined, all terms (including technical and scientificterms) used herein have the same meaning as commonly understood by oneof ordinary skill in the art to which this disclosure belongs. It willbe further understood that terms, such as those defined in commonly useddictionaries, should be interpreted as having a meaning that isconsistent with their meaning in the context of the relevant art and thepresent disclosure, and will not be interpreted in an idealized oroverly formal sense unless expressly so defined herein.

Exemplary embodiments are described herein with reference to crosssection illustrations that are schematic illustrations of idealizedembodiments. As such, variations from the shapes of the illustrations asa result, for example, of manufacturing techniques and/or tolerances,are to be expected. Thus, embodiments described herein should not beconstrued as limited to the particular shapes of regions as illustratedherein but are to include deviations in shapes that result, for example,from manufacturing. For example, a region illustrated or described asflat may, typically, have rough and/or nonlinear features. Moreover,sharp angles that are illustrated may be rounded. Thus, the regionsillustrated in the figures are schematic in nature and their shapes arenot intended to illustrate the precise shape of a region and are notintended to limit the scope of the present claims.

According to an aspect of the present disclosure, a composite membraneincludes an ion-conductive polymer layer and a plurality of gas blockinginorganic particles non-continuously aligned on the ion-conductivepolymer layer, wherein the composite membrane has a radius of curvatureof about 10 millimeters (mm) or less.

In an embodiment, the composite membrane may have a radius of curvatureof about 5 mm or less, about 4 mm or less, about 3 mm or less, about 2mm or less, about 1.8 mm or less, about 1.6 mm or less, about 1.4 mm orless, about 1.2 mm or less, about 1 mm or less, about 0.9 mm or less,about 0.8 mm or less, about 0.7 mm or less, about 0.6 mm or less, about0.5 mm or less, about 0.4 mm or less, about 0.3 mm or less, about 0.2 mmor less, or about 0.1 mm or less, and in another embodiment, about 0.1mm to about 5 mm, about 0.1 mm to about 4 mm, about 0.1 mm to about 3mm, about 0.1 mm to about 2 mm, about 0.1 mm to about 1 mm, about 0.2 mmto about 1 mm, about 0.3 mm to about 1 mm, about 0.4 mm to about 1 mm,about 0.5 mm to about 1 mm, about 0.6 mm to about 1 mm, about 0.7 mm toabout 1 mm, about 0.8 mm to about 1 mm, about 0.9 mm to about 1 mm,about 1 mm to about 2 mm, about 1.2 mm to about 2 mm, about 1.4 mm toabout 2 mm, about 1.6 mm to about 2 mm, about 1.8 mm to about 2 mm,about 2 mm to about 2.2 mm, about 2 mm to about 2.4 mm, about 2 mm toabout 2.6 mm, about 2 mm to about 2.8 mm, about 2 mm to about 3 mm,about 2 mm to about 4 mm, about 3 mm to about 4 mm, or about 2 mm toabout 5 mm, and thus may have improved flexibility. Accordingly, thecomposite membrane may be used in a foldable battery.

As used herein, the term “radius of curvature” may refer to a radius ofa circle formed by bending a film, e.g., the composite membrane. Agreater radius of curvature indicates a lesser degree of bending, and alesser radius of curvature indicates a greater degree of bending. Thesmaller a radius of curvature is, the greater the flexibility of acomposite membrane may be. In geometric terms, the term “the radius ofcurvature” refers to a radius of a circle, the curvature of which isequal to that of a curve at a given point. A larger radius of curvaturemeans a lesser degree of curvature and a smaller radius of curvaturemeans a greater degree of curvature.

A radius of curvature limit may refer to a radius of curvature at amaximum degree of bending that a material can sustain, for example amaximum degree of curvature. FIG. 3C is a perspective view illustratingthe radius of curvature R of a composite membrane 100 according to anembodiment. The composite membrane 100 may have a limit of a radius ofcurvature R of about 5 mm or less, about 4 mm or less, about 3 mm orless, about 2 mm or less, about 1.8 mm or less, about 1.6 mm or less,about 1.4 mm or less, about 1.2 mm or less, about 1 mm or less, about0.9 mm or less, about 0.8 mm or less, about 0.7 mm or less, about 0.6 mmor less, about 0.5 mm or less, about 0.4 mm or less, about 0.3 mm orless, about 0.2 mm or less, or about 0.1 mm or less, and may be about0.1 mm to about 5 mm, about 0.1 mm to about 4 mm, about 0.1 mm to about3 mm, about 0.1 mm to about 2 mm, about 0.1 mm to about 1 mm, about 0.2mm to about 1 mm, about 0.3 mm to about 1 mm, about 0.4 mm to about 1mm, about 0.5 mm to about 1 mm, about 0.6 mm to about 1 mm, about 0.7 mmto about 1 mm, about 0.8 mm to about 1 mm, about 0.9 mm to about 1 mm,about 1 mm to about 2 mm, about 1.2 mm to about 2 mm, about 1.4 mm toabout 2 mm, about 1.6 mm to about 2 mm, about 1.8 mm to about 2 mm,about 2 mm to about 2.2 mm, about 2 mm to about 2.4 mm, about 2 mm toabout 2.6 mm, about 2 mm to about 2.8 mm, about 2 mm to about 3 mm,about 2 mm to about 4 mm, about 3 mm to about 4 mm, or about 2 mm toabout 5 mm. The radius of curvature limit refers to a radius ofcurvature when the composite membrane has a maximum degree of bending,for example a maximum degree of curvature. When the limit of the radiusof curvature R of the composite membrane 100 is within this range, thereis effectively no limitation in bending when used a battery includingthe composite membrane. In other words, the radius of curvature limitrefers to a radius of curvature when the composite membrane has amaximum degree of bending.

A composite membrane according to an embodiment of the presentdisclosure may have an improved oxygen blocking ability, reduced weight,and improved energy density per weight, as compared with a polymerelectrolyte for a lithium air battery.

The composite membrane may include a sea-island structure ofdiscontinuously aligned gas blocking inorganic particles in a continuousion-conductive polymer layer, or an alternately aligned structure inwhich the gas blocking inorganic particles are aligned to alternate withion-conductive polymer layers in a horizontal cross-section of thecomposite membrane.

In an embodiment, as illustrated in FIG. 1A, the composite membrane mayhave a structure in which the gas blocking inorganic particles 11 aredisposed, e.g., aligned, on a surface of the ion-conductive polymerlayer 10. In this structure, the gas blocking inorganic particles 11 maybe non-continuously disposed so that the individual gas blockinginorganic particles 11 are separated from each other on theion-conductive polymer layer 10, preventing the formation of anagglomeration of the gas blocking inorganic particles 11. Theagglomeration of gas blocking inorganic particles 11 is undesirablebecause the agglomerate may increase the electrical resistance andreduce lithium ion conductivity of the composite membrane. Asillustrated in FIG. 1A, the gas blocking inorganic particles 11 may bealigned in a substantially horizontal direction on the ion-conductivepolymer layer 10. In an embodiment, at least a portion of the surface ofat least one of the gas blocking inorganic particles 11 is notsurrounded by the ion-conductive polymer layer 10.

A lithium air battery manufactured using the composite membrane may havea structure in which the gas blocking inorganic particles are disposedin a region of the composite membrane adjacent to a cathode of thelithium air battery. Without being bound by theory, when a lithium airbattery has such a structure, reaction of lithium in a lithium anodewith the gas blocking inorganic particles may be effectively suppressedeven when the gas blocking inorganic particles are reactive withlithium, and thus the composite membrane may serve as a protective layerfor the lithium anode and as an effective gas blocking layer.

Referring to FIG. 1B, the composite membrane may have a structure inwhich the gas blocking inorganic particles 11 are disposed within theion-conductive polymer layer 10. In this structure, the gas blockinginorganic particles 11 may be non-continuously disposed so that theindividual gas blocking inorganic particles 11 may be separated fromeach other, e.g., spaced apart from each other, in the ion-conductivepolymer layer 10, preventing and/or reducing the formation of anagglomeration of gas blocking inorganic particles, which can result inresistance against lithium ion conduction. In an embodiment, at leastone of the gas blocking inorganic particles 11 is substantially enclosedwithin the ion-conductive polymer layer 10 such that the gas blockinginorganic particle 11 is surrounded by the ion-conductive polymer layer10.

In a lithium air battery, when external oxygen reaches the lithium metalthrough a cathode and an electrolyte, a lithium oxide (LiO₂ or Li₂O₂)may be produced so as to remarkably reduce a lifetime of the lithium airbattery.

To address this drawback, a composite membrane according to anembodiment may be disposed between a cathode electrolyte and an anodeelectrolyte, e.g., between a cathode and an anode, as a gas blockinglayer. This arrangement of the composite membrane may improve thelifetime of the lithium air battery. The composite membrane may belightweight and flexible, have improved ion conductivity, and have alarge size. Due to the arrangement of the composite membrane, the gasblocking inorganic particle 11 may be effective in blocking the oxygencoming from the cathode, thereby protecting the anode.

In an example embodiment, the gas blocking inorganic particle 11 mayhave a hydrophobic coating layer on at least one surface thereof. Thehydrophobic coating layer may be a continuous coating layer or anon-continuous coating layer inclusive of an island shaped coatinglayer. When the gas blocking inorganic particle 11 has a hydrophobiccoating layer on at least one surface thereof, the gas blockinginorganic particles in a non-continuously aligned arrangement may beeffectively formed without agglomeration of the gas blocking inorganicparticles. In other words, the hydrophobic coating layer on at least onesurface of the gas inorganic particles may reduce or eliminateagglomeration of the gas blocking inorganic particles.

The hydrophobic coating layer on at least one surface of the gasblocking inorganic particles may be identified by X-ray photoelectronspectroscopy (XPS), for example, from the presence of the Si 2p and C 1speaks in XPS spectra.

The hydrophobic coating layer may comprise, and in an embodiment consistof, a condensation reaction product of at least one selected fromcompounds represented by Formula 1.

In Formula 1, R₁ to R₃ may each independently be selected from asubstituted or unsubstituted C1-C20 alkyl group, a substituted orunsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, asubstituted or unsubstituted C6-C20 aryl group, a substituted orunsubstituted C7-C20 arylalkyl group, a substituted or unsubstitutedC6-C20 aryloxy group, a substituted or unsubstituted C2-C20 heteroarylgroup, a substituted or unsubstituted C2-C20 heteroaryloxy group, asubstituted or unsubstituted C3-C20 heteroarylalkyl group, a substitutedor unsubstituted C2-C20 heterocyclic group, and a halogen atom; and R₄may be selected from hydrogen, a substituted or unsubstituted C1-C20alkyl group, and a substituted or unsubstituted C6-C20 aryl group.

For example, R₁ to R₃ may each independently be selected from methyl,ethyl, butyl, isobutyl, octyl, methoxy, ethoxy, octadecyl,3-methacryloxypropyl, decyl, propyl, and chlorine. For example, R₄ maybe selected from methyl, ethyl, butyl, propyl, isobutyl, and octyl.

For example, the compound represented by Formula 1 may include at leastone compound selected from isobutyltrimethoxysi lane,octyltrimethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane,dodecyltrimethoxysilane, octadecyltrimethoxysilane,3-methacryloxypropyltrimethoxysilane, n-octadecyltriethoxysilane,1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFO), and(3-mercaptopropyl)trimethoxysilane.

An alignment of the gas blocking inorganic particles in the compositemembrane may vary depending on the composition of the hydrophobiccoating layer.

For example, when the hydrophobic coating layer includes a condensationproduct of exclusively PFO, the composite membrane may have a structureas illustrated in FIG. 1B in which the gas blocking inorganic particlesare present within the ion-conductive polymer layer 10.

For example, when the hydrophobic coating layer includes a condensationproduct that is derived from a mixture of PFO and(3-mercaptopropyl)trimethoxysilane, unlike when the hydrophobic coatinglayer includes a condensation product derived from only PFO, e.g.,without (3-mercaptopropyl)trimethoxysilane, the composite membrane mayhave a structure as illustrated in FIG. 1A in which the gas blockinginorganic particles 11 are present on the upper surface of the compositemembrane.

For example, an amount of the condensation reaction product of at leastone of the compounds represented by Formula 1 in the hydrophobic coatinglayer may be from about 0.1 parts to about 30 parts by weight, based on100 parts by weight of the gas blocking inorganic particles, and in anembodiment, from about 0.1 parts to about 10 parts by weight, and inanother embodiment, from about 0.1 parts to about 5 parts by weight,based on 100 parts by weight of the gas blocking inorganic particles.

In an embodiment, the gas blocking inorganic particles in theion-conductive polymer layer may be non-continuously aligned as amonolayer, for example on the surface of ion-conductive polymer layer orwithin the ion-conductive polymer layer. The gas blocking inorganicparticles may be in a single-particle state and without a grainboundary. Accordingly, no grain boundary may be observed in the gasblocking inorganic particles. The ion-conductive polymer layer may be adense layer having non-porous characteristics.

When a composite membrane according to any of the above-describedembodiments is used as a gas barrier membrane blocking moisture or gas(for example, oxygen or carbon dioxide) in a lithium air battery, ions(for example, lithium ions) may pass through the ion-conductive polymerlayer including the gas blocking inorganic particles, while moisture orgas (for example, oxygen or carbon dioxide) may be blocked by theion-conductive polymer layer.

In an embodiment, the gas blocking inorganic particles in the compositemembrane may occupy about 70% or more of a total area of the compositemembrane, for example, about 70% to about 99%, about 70% to about 90%,or about 70% to about 80% of a total area of the composite membrane,where the percentage of the total area of the composite membraneoccupied may be determined based on a percentage of the cross-sectionalarea of the composite membrane occupied by a projection of the gasblocking inorganic particles on the composite membrane. When the gasblocking inorganic particles occupy the cross-sectional area of thecomposite membrane within these ranges, the composite membrane may havean improved gas blocking ability.

As used herein, the term “gas” may be construed as meaning at least oneselected from oxygen, carbon dioxide, moisture, and vapor, e.g., watervapor. For example, gas permeability may refer to, for example, oxygenpermeability or moisture permeability.

The alignment of the gas blocking inorganic particles is not limited toalignments illustrated in the embodiments of FIGS. 1A and 1B.

The gas blocking inorganic particles may have any of a variety ofsuitable shapes, may be rectilinear or curvilinear, and may comprise forexample, vertical and horizontal cross-sectional shapes, such as acircular shape, a triangular shape, a quasi-triangular shape, atriangular shape with semi-circles, a triangular shape with a roundedcorner, a square shape, a rectangular shape, a rectangular shape withsemi-circles, and a polygonal shape. For example, the gas blockinginorganic particles may have any of a variety of shapes, such as a cubicshape, a spherical shape, a circular shape, an elliptical shape, a rodshape, a stick shape, a tetrahedral shape, a pyramidal shape, anoctahedral shape, a cylindrical shape, a polygonal shape, a pillarshape, a polygonal pillar-like shape, a conical shape, a columnar shape,a tubular shape, a helical shape, a funnel shape, a dendritic shape, ora bar shape.

The size of the gas blocking inorganic particles may refer to an averagediameter thereof when the gas blocking inorganic particles have aspherical shape or a length of a major (longer) axis when the gasblocking inorganic particles have any other shapes.

In a lithium air battery, a ceramic material layer has been used forboth the functions of ion conduction and oxygen blocking. However, aceramic material layer has a high weight and a limited shape, and isdifficult to form in a large size. Moreover, a ceramic material layerhas a weak mechanical strength and is easily broken by external impacts,and weight or thickness reduction is limited. These drawbacks in using aceramic material layer obstruct practical application.

In an embodiment, the composite membrane may have gas blocking inorganicparticles non-continuously aligned without agglomeration of the gasblocking inorganic particles, as illustrated in FIGS. 1A and 1B. Thisstructure may provide a migration path of lithium ions and ensuresimproved ion conductivity. Unlike a ceramic material, the compositemembrane may also be formed as a thin film, and thus may have reducedelectrical resistance and reduced weight, and may be formed in a largesize. Furthermore, the composite membrane may have improved flexibilitydue to the inclusion of a polymer, improved processibility applicable toany suitable cell design, and improved mechanical strength. Compared toa ceramic material layer, the composite membrane may be prepared atlower cost. By using a composite membrane according to any of theembodiments disclosed herein, a large-area, thin-film, and light-weightlithium air battery having an improved lifetime may be manufacturedthrough a process as described herein.

For example, the amount of the gas blocking inorganic particles may befrom about 10 parts to about 90 parts by weight, and in an embodiment,about 20 parts to about 80 parts by weight, based on 100 parts by weightof a total weight of the composite membrane. When the amount of the gasblocking inorganic particles is within these ranges, the compositemembrane may have improved ion conductivity and improved mechanicalstrength.

The gas blocking inorganic particles may further include at least oneselected from a glassy active metal ionic conductor, an amorphous activemetal ionic conductor, a ceramic active metal ionic conductor, and aglass-ceramic active metal ionic conductor.

In an embodiment, the gas blocking inorganic particles may comprise anoxide-based lithium ion-conductive solid ceramic electrolyte. Forexample, the gas blocking inorganic particles may be at least oneselected from Li_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂ (wherein 0<x<2and 0≤y<3), BaTiO₃, Pb(Zr_(r)Ti_(1−r))O₃ (PZT) (wherein 0≤r≤1),Pb_(1−x)La_(x)Zr_(1−y)Ti_(y)O₃ (PLZT) (wherein 0≤x<1, and 0≤y<1),Pb(Mg₃Nb_(2/3))O₃—PbTiO₃ (PMN-PT), HfO₂, SrTiO₃, SnO₂, CeO₂, Na₂O, MgO,NiO, CaO, BaO, ZnO, ZrO₂, Y₂O₃, Al₂O₃, TiO₂, SiO₂, SiC, lithiumphosphate (Li₃PO₄), lithium titanium phosphate (Li_(x)Ti_(y)(PO₄)₃,wherein 0<x<2 and 0<y<3), lithium aluminum titanium phosphate(Li_(x)Al_(y)Ti_(z)(PO₄)₃, wherein 0<x<2, 0<y<1, and 0<z<3),Li_(1+x+y)(Al_(q)Ga_(1−q))_(x)(Ti_(h)Ge_(1−h))_(2−x)Si_(y)P_(3−y)O₁₂(wherein 0≤q≤1 and 0≤y≤1), lithium lanthanum titanate (Li_(x)La_(y)TiO₃,wherein 0<x<2 and 0<y<3), lithium germanium thiophosphate(Li_(x)Ge_(y)P_(z)S_(w), wherein 0<x<4, 0<y<1, 0<z<1, and 0<w<5),lithium nitride glass (Li_(x)N_(y), wherein 0<x<4 and 0<y<2), SiS₂ glass(Li_(x)Si_(y)S_(z), wherein 0≤x<3, 0<y<2, and 0<z<4), P₂S₅ glass(Li_(x)P_(y)S_(z), wherein 0≤x<3, 0<y<3, and 0<z<7), Li₂O, LiF, LiOH,Li₂CO₃, LiAlO₂, Li₂O—Al₂O₃—SiO₂—P₂O₅—TiO₂—GeO₂ ceramics, and Garnetceramics (Li_(3+x)La₃M₂O₁₂, wherein M is Te, Nb, or Zr, and x is aninteger from 1 to 10). An example of the Garnet ceramics may beLi₇La₃Zr₂O₁₂.

For example, the gas blocking inorganic particles may includeL_(1.4)Ti_(1.6)Al_(0.4)P₃O₁₂ (LTAP) or a Li₂O—Al₂O₃—SiO₂—P₂O₅—TiO₂—GeO₂ceramic.

As described above, the gas blocking inorganic particles havesubstantially no grain boundary, which thus may ensure a lithiumconduction path with a reduced electrical resistance in the compositemembrane including the gas blocking inorganic particles. This mayfacilitate conduction and migration of lithium ions, and may also resultin markedly improved lithium ion conductivity and lithium iontransference rate. Compared with a membrane including only inorganicparticles, a composite membrane according to an embodiment may haveimproved flexibility and mechanical strength.

In an embodiment, the gas blocking inorganic particles may be in theform of a single-particle state without a grain boundary, which may beidentified by scanning electron microscopy (SEM).

For example, the gas blocking inorganic particles may have an averageparticle diameter of about 1 micrometer (μm) to about 300 μm, and in anexample embodiment, about 1 μm to about 200 μm, and in another exampleembodiment, about 1 μm to about 150 μm, or about 1 μm to about 100 μm,or about 1 μm to about 90 μm, or about 1 μm to about 80 μm, or about 1μm to about 70 μm, or about 1 μm to about 60 μm, or about 1 μm to about50 μm, or about 1 μm to about 40 μm, or about 1 μm to about 30 μm, orabout 1 μm to about 20 μm, or about 1 μm to about 10 μm. In anotherembodiment, the gas blocking inorganic particles may have an averageparticle diameter of less than about 300 μm, or less than about 200 μm,or less than about 150 μm, or less than about 100 μm, or less than about90 μm, or less than about 80 μm, or less than about 70 μm, or less thanabout 60 μm, or less than about 50 μm, or less than about 40 μm, or lessthan about 30 μm, or less than about 20 μm, or less than about 10 μm.When the gas blocking inorganic particles have an average particlediameter within these ranges, the composite membrane including the gasblocking inorganic particles may be prepared in a single-particle statewithout a grain boundary through, for example, a grinding process.

The particle sizes of the gas blocking inorganic particles may besubstantially uniform, which may be maintained in the compositemembrane. For example, the gas blocking inorganic particles may have aD50 of about 110 μm to about 130 μm, a D90 of about 180 μm to about 200μm, and a D10 of about 60 μm to about 80 μm. The terms “D50”, “D10”, and“D90” refer to a particle diameter of 50 volume %, 10 volume %, and 90volume %, respectively, in a cumulative distribution curve of particlesizes (particle diameters).

The ion-conductive polymer layer of the composite membrane may include apolymer having barrier characteristics rendering it capable of blockingat least one selected from oxygen and moisture, as well as anodecorrosive gases. The anode corrosive gases may be, for example, vapor,carbon dioxide, or oxygen. Therefore, the composite membrane includingthe ion-conductive polymer layer may also serve as an oxygen barriermembrane, a moisture blocking membrane, or a carbon dioxide barriermembrane.

For example, the polymer of the ion-conductive polymer layer may includeat least one selected from polyethylene oxide, polyvinylidene fluoride,polyvinylpyrrolidone, polyvinyl alcohol, poly 2-vinylpyridine,polytetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylenecopolymer, polychlorotrifluoroethylene, a perfluoroalkoxy copolymer, afluorinated cyclic ether, polyethylene oxide diacrylate, polyethyleneoxide dimethacrylate, polypropylene oxide diacrylate, polypropyleneoxide dimethacrylate, polymethyleneoxide diacrylate, polymethyleneoxidedimethacrylate, poly(C1-C4 alkyldiol diacrylate, poly(C1-C4 alkyl)dioldimethacrylate, polydivinylbenzene, polyether, polycarbonate, polyamide,polyester, polyvinyl chloride, polyimide, polycarboxylic acid,polysulfonic acid, polysulfone, polystyrene, polyethylene,polypropylene, poly(p-phenylene), polyacetylene, poly(p-phenylenevinylene), polyaniline, polypyrrole, polythiophene, polyacene,poly(naphthalene-2,6-diyl), polypropylene oxide, a vinylidenefluoride-hexafluoropropylene copolymer, poly(vinyl acetate), poly(vinylbutyral-co-vinyl alcohol-co-vinyl acetate), poly(methylmethacrylate-co-ethyl acrylate), polyacrylonitrile, polyvinylchloride-co-vinyl acetate, poly(l-vinyl pyrrolidone-co-vinyl acetate),poly(C1-C6 alkyl)acrylate, poly(C1-C6 alkyl)methacrylate, polyurethane,polyvinyl ether, an acrylonitrile-butadiene rubber, a styrene-butadienerubber, an acrylonitrile-butadiene-styrene rubber, a sulfonatedstyrene/ethylene-butylene triblock copolymer, epoxide resin, and apolymer obtained from at least one acrylate monomer selected fromethoxylated neopentyl glycol diacrylate, ethoxylated bisphenol Adiacrylate, a C10-C30 alkyl acrylate, ethoxylated aliphatic urethaneacrylate, and ethoxylated C2-C20 alkylphenol acrylate.

In a composite membrane according to an embodiment, the amount of thepolymer in the ion-conductive polymer layer may be from about 10 partsto about 80 parts by weight, and in another example embodiment, about 50parts to about 80 parts by weight, based on 100 parts by weight of atotal weight of the composite membrane. When the amount of the polymerin the ion-conductive polymer is within these ranges, the compositemembrane may have improved lithium ion conductivity, flexibility, andgas blocking ability without deterioration in film formability.

The ion-conductive polymer may have a weight average molecular weight ofabout 10,000 to about 300,000 Daltons, as measured by gel permeationchromatography (GPC), e.g., using a polystyrene standard. When thepolymer has a weight average molecular weight within this range, thecomposite membrane may have improved ion conductivity and improved gasand moisture blocking ability without deterioration in film formability.

In an embodiment, the composite membrane may include the gas blockinginorganic particles with a high density, and thus may have reducedelectrical resistance.

For example, the composite membrane may have a weight of about 5milligrams per square centimeter (mg/cm²) to about 20 mg/cm², and inanother embodiment, about 11 mg/cm² to about 16 mg/cm². When thecomposite membrane has a weight within these ranges, a thin-film,lightweight lithium air battery may be manufactured using the compositemembrane.

For example, the composite membrane may have a thickness of about 10 μmto about 200 μm, and in another embodiment, a thickness of about 70 μmto about 100 μm. When the composite membrane has a thickness withinthese ranges, the composite membrane may have improved ion conductivityand improved moisture and gas blocking ability.

In an embodiment, the composite membrane may further include a porousbase, for example a porous substrate. The porous base may be anysuitable base including pores and having suitable mechanical andheat-resistance characteristics. Examples of the porous base are sheetsor nonwoven fabric including an olefin-based polymer, glass fiber, orpolyethylene having suitable chemical resistance and hydrophobiccharacteristics. Examples of the olefin-based polymer include at leastone selected from polyethylene and polypropylene.

For example, the porous base may be a mixed multi-layer, such as atwo-layered polyethylene/polypropylene separator, a three-layeredpolyethylene/polypropylene/polyethylene separator, or a three-layeredpolypropylene/polyethylene/polypropylene separator. For example, theporous base may include a polyethylene layer or a polypropylene layer.The porous base may have a pore diameter of about 0.01 μm to about 10μm, and a thickness of about 5 μm to about 35 μm. The porous base mayinclude a liquid electrolyte including a lithium salt and an organicsolvent.

In an embodiment, the composite membrane may further include at leastone selected from a lithium salt, an ionic liquid, and a polymeric ionicliquid.

The amount (concentration) of the lithium salt may be from about 0.01moles per liter (molar, M) to about 5 M, and in another embodiment, fromabout 0.2 M to about 2.0 M. When the amount of the lithium salt iswithin these ranges, the composite membrane may have improvedconductivity.

The lithium salt may serve as a source of lithium ions in a battery bybeing dissolved in a solvent. The lithium salt may be at least oneselected from LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiN(SO₂C₂F₅)₂, Li(CF₃SO₂)₂N,Li(FSO₂)₂N, LiC₄F₉SO₃, LiClO₄, LiAlO₂, LiAlCl₄,LiN(C_(x)F_(2x+1)SO₂)(C_(y)F_(2y+1)SO₂) (wherein x and y are naturalnumbers), LiF, LiBr, LiCl, LiOH, LiI, and LiB(C₂O₄)₂ (LiBOB; lithiumbis(oxalato) borate).

In an embodiment, the composite membrane may further include at leastone selected from an ionic liquid and a polymeric ionic liquid, inaddition to a lithium salt as described above.

An ionic liquid refers to a salt in a liquid state at room temperatureor a fused salt at room temperature that includes ions having a meltingpoint equal to or less than room temperature. The ionic liquid may be atleast one selected from compounds each including i) a cation of at leastone selected from an ammonium cation, a pyrrolidinium cation, apyridinium cation, a pyrimidinium cation, an imidazolium cation, apiperidinium cation, a pyrazolium cation, an oxazolium cation, apyridazinium cation, a phosphonium cation, a sulfonium cation, and atriazolium cation; and ii) at least one anion selected from BF₄ ⁻, P F₆⁻, ASF₆ ⁻, SbF₆ ⁻, AlCl₄ ⁻, HSO₄ ⁻, ClO₄ ⁻, CH₃SO₃ ⁻, CF₃CO₂ ⁻,(CF₃SO₂)₂N⁻, (FSO₂)₂N⁻, Cl⁻, Br⁻, I⁻, SO₄ ⁻, CF₃SO₃ ⁻, (C₂F₅SO₂)₂N⁻, and(C₂F₅SO₂)(CF₃SO₂)N⁻.

Examples of the ionic liquid may be compounds including at least onecation of a linear or branched substituted ammonium, imidazolium,pyrrolidinium, pyridinium, and piperidinium; and at least one anionselected from PF₆ ⁻, BF₄ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N⁻, (C₂F₅SO₂)₂N⁻,(FSO₂)₂N⁻, and(CN)₂N⁻.

For example, the ionic liquid may comprise at least one selected from N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, N-methyl-N-propylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide, and 1-ethyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide.

For example, the polymeric ionic liquid may comprise, for example, apolymerization product of ionic liquid monomers, or a polymericcompound. The polymeric ionic liquid is highly soluble in an organicsolvent, and thus may further improve the ionic conductivity of theelectrolyte when added.

When the ionic liquid is a polymeric ionic liquid obtained bypolymerization of ionic liquid monomers as described above, a resultingproduct from the polymerization reaction may be washed and dried,followed by an anionic substitution reaction to prepare an appropriatecomposite membrane that may improve solubility in an organic solvent.

In an embodiment, the polymeric ionic liquid may include a repeatingunit that includes i) a cation of at least one selected from an ammoniumcation, a pyrrolidinium cation, a pyridinium cation, a pyrimidiniumcation, an imidazolium cation, a piperidinium cation, a pyrazoliumcation, an oxazolium cation, a pyridazinium cation, a phosphoniumcation, a sulfonium cation, and a triazolium cation; and ii) at leastone anion selected from BF₄ ⁻, PF₆ ⁻, ASF₆ ⁻, SbF₆ ⁻, AlCl₄ ⁻, HSO₄ ⁻,ClO₄ ⁻, CH₃SO₃ ⁻, CF₃CO₂ ⁻, (CF₃SO₂)₂N⁻, (FSO₂)₂N⁻, Cl⁻, Br⁻, I⁻, SO₄ ⁻,CF₃SO₃ ⁻, (C₂F₅SO₂)₂N⁻, (C₂F₅SO₂)(CF₃SO₂)N⁻, NO₃ ⁻, Al₂Cl₇ ⁻,(CF₃SO₂)₃C⁻, (CF₃)₂PF₄ ⁻, (CF₃)₃PF₃ ⁻, (CF₃)₄PF₂ ⁻, (CF₃)₅PF⁻, (CF₃)₆P⁻,SF₆CF₂SO₃ ⁻, SF₅CHFCF₂SO₃ ⁻, CF₃CF₂(CF₃)₂CO⁻, (CF₃SO₂)₂CH⁻, SF₅)₃C⁻, and(O(C F₃)₂C₂(CF₃)₂O)₂PO⁻.

In another embodiment, the polymeric ionic liquid may be prepared bypolymerization of ionic liquid monomers. The ionic liquid monomers mayhave a polymerizable functional group such as at least one selected froma vinyl group, an allyl group, an acrylate group, and a methacrylategroup, and may include a cation of at least one selected from anammonium cation, a pyrrolidinium cation, a pyridinium cation, apyrimidinium cation, an imidazolium cation, a piperidinum cation, apyrazolium cation, an oxazolium cation, a pyridazinium cation, aphosphonium cation, a sulfonium cation, and a triazolium cation, and atleast one of the above-listed anions.

Non-limiting examples of the ionic liquid monomers are1-vinyl-3-ethylimidazolium bromide, a compound represented by Formula 5,and a compound represented by Formula 6.

For example, the polymeric ionic liquid may be a compound represented byFormula 7 or a compound represented by Formula 8.

In Formula 7, R₁ and R₃ may each independently be selected from ahydrogen, a substituted or unsubstituted C1-C30 alkyl group, asubstituted or unsubstituted C2-C30 alkenyl group, a substituted orunsubstituted C2-C30 alkynyl group, a substituted or unsubstitutedC6-C30 aryl group, a substituted or unsubstituted C2-C30 heteroarylgroup, and a substituted or unsubstituted C4-C30 carbocyclic group; R₂may be selected from a chemical bond, a C1-C30 alkylene group, a C6-C30arylene group, a C2-C30 heteroarylene group, and a divalent C4-C30carbocyclic group; X⁻ indicates an anion of the polymeric ionic liquid;and n may be a number from about 500 to about 2800.

In Formula 8, Y⁻ may be defined the same as X⁻ in Formula 7; and n maybe a number from about 500 to about 2800. For example, in Formula 8, Y⁻may be selected from bis(trifluoromethanesulfonyl)imide (TFSI), BF₄, andCF₃SO₃.

The polymeric ionic liquid may include, for example, at least one cationselected from poly(l-vinyl-3-alkylimidazolium),poly(l-allyl-3-alkylimidazolium), andpoly(1-(methacryloyloxy-3-alkylimidazolium), and at least one anionselected from CH₃COO⁻, CF₃COO⁻, CH₃SO₃ ⁻, CF₃SO₃ ⁻, (CF₃SO₂)₂N₇(FSO₂)₂N⁻, (CF₃SO₂)₃C⁻, (CF₃CF₂SO₂)₂N⁻, C₄F₉S O₃ ⁻, C₃F₇COO⁻, and(CF₃SO₂)(CF₃CO)N⁻.

For example, the compound represented by Formula 8 may bepolydiallyldimethyl ammonium bis(trifluoromethanesulfonyl)imide.

For example, the polymeric ionic liquid may be at least one selectedfrom poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide(TFSI), poly(l-methacryloyloxy propyl-3-methylimidazolium)bis(trifluoromethanesulfonyl) imide), andpoly(l-vinyl-3-ethylimidazolium) bis(trifluoromethanesulfonyl) imide).

In another embodiment, the polymeric ionic liquid may include alow-molecular weight polymer, a thermally stable ionic liquid, and alithium salt. The low-molecular weight polymer may have an ethyleneoxide chain. The low-molecular weight polymer may be a glyme.Non-limiting examples of the glyme may be at least one selected frompolyethylene glycol dimethylether (polyglyme), tetraethylene glycoldimethyl ether (tetraglyme), and triethylene glycol dimethylether(triglyme).

For example, the low-molecular weight polymer may have a weight averagemolecular weight of about 75 to about 2000 Daltons (Da), and in anotherembodiment, about 250 to about 500 Da. The thermally stable ionic liquidmay be defined the same as any of the ionic liquids described above.

Hereinafter, a method of preparing a composite membrane, according to anexample embodiment, will be described.

An ion-conductive polymer and an organic solvent may be mixed to preparean ion-conductive layer forming composition. At least one selected froma lithium salt, an ionic liquid, and a polymeric ionic liquid may befurther added to the ion-conductive layer forming composition.

Referring to FIG. 2 , an ion-conductive polymer layer 20 in a liquidstate, for example dissolved in or mixed with an organic solvent, may beon a separator 22. The ion-conductive polymer layer 20 in a liquid statemay be formed by applying the ion-conductive polymer layer formingcomposition and then the gas blocking inorganic particles 21 onto theseparator 22. The gas blocking inorganic particles 21 may be particlestreated to be hydrophobic by forming a hydrophobic coating layer on atleast one surface thereof. The gas blocking inorganic particles 21having the hydrophobic coating layers on at least one surface thereofmay be non-continuously aligned without agglomeration on the uppersurface, lower surface, or inside of the ion-conductive polymer layer20.

Subsequently, the resulting structure may be dried, thereby preparing acomposite membrane 23 according to another example embodiment.

The drying of the resulting structure whereby the organic solvent isremoved may be performed, for example, at a temperature of about roomtemperature (e.g., 25° C.) to about 60° C. As the organic solvent isremoved, the gas blocking inorganic particles 11 having the hydrophobiccoating layers may remain on the ion-conductive polymer layer 20.

For example, the organic solvent of the ion-conductive layer formingcomposition may be at least one selected from N-methylpyrrolidone (NMP),methanol, ethanol, chloroform, methylene chloride, methyl ethyl ketone,acetonitrile, acetone, formamide, dimethyl formamide, tetrahydrofuran,N-methyl-2-pyrrolidone, dimethyl sulfoxide, 1,3-dioxolane, sulfolane,dimethyl sulfolane, ethyl acetate, benzene, toluene, 1,2-dichloroethane,and hexanes.

The gas blocking inorganic particles having a hydrophobic coating layeron at least one surface thereof may be prepared by reacting the gasblocking inorganic particles with a compound represented by Formula 1;and washing and drying the resulting reaction product.

In Formula 1, R₁ to R₃ may each independently be selected from asubstituted or unsubstituted C1-C20 alkyl group, a substituted orunsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, asubstituted or unsubstituted C6-C20 aryl group, a substituted orunsubstituted C7-C20 arylalkyl group, a substituted or unsubstitutedC6-C20 aryloxy group, a substituted or unsubstituted C2-C20 heteroarylgroup, a substituted or unsubstituted C2-C20 heteroaryloxy group, asubstituted or unsubstituted C3-C20 heteroarylalkyl group, a substitutedor unsubstituted C2-C20 heterocyclic group, and a halogen atom; and R₄may be selected from hydrogen, a substituted or unsubstituted C1-C20alkyl group, and a substituted or unsubstituted C6-C20 aryl group.

The gas blocking inorganic particles may be prepared through grindingand sieving such that an average particle diameter is about 1 μm toabout 300 μm, and in another example embodiment, about 1 μm to about 200μm, and in still another example embodiment, about 1 μm to about 100 μm.

The size of the gas blocking inorganic particles is a factor related tothe ion conductivity of the composite membrane. Accordingly, the size ofthe gas blocking inorganic particles may be appropriately controlled tobe uniform. To this end, gas blocking inorganic particles having adesired average particle diameter may be collected through sieving.

For example, the gas blocking inorganic particles may have an averageparticle diameter of about 1 μm to about 300 μm, and in another exampleembodiment, about 1 μm to about 200 μm, and in still another exampleembodiment, about 1 μm to about 100 μm. In another example embodiment,the gas blocking inorganic particles may have an average particlediameter of about 90 μm to about 200 μm, and in another exampleembodiment, about 90 μm to about 100 μm. The gas blocking inorganicparticles may have an average particle diameter as defined hereinabove.

In an embodiment, the gas blocking inorganic particles may be preparedthrough grinding and further sorting to have an average particlediameter of about 1 μm to about 300 μm, before undergoing a reactionwith the compound of represented by Formula 1.

The grinding may be performed using, for example, a bead mill. Beadsused in the grinding may have a diameter of, for example, about 0.5 mmto about 2 mm, and the speed of rotation of a grinder may be, forexample, from about 1000 revolutions per minute (rpm) to about 2000 rpm.When the diameter of the beads and the speed of rotation of the grinderare within these ranges, pulverization of the gas blocking inorganicparticles which may be, for example, lithium-titanium-aluminum-phosphate(LTAP, Li_(1.4)Ti_(1.6)Al_(0.4)P₃O₁₂), may be inhibited.

For example, the beads may be zirconia beads or alumina beads. However,embodiments are not limited thereto.

The reacting of the gas blocking inorganic particles with the compoundrepresented by Formula 1 may be performed by immersion, spray, or ballmilling.

In an embodiment, the reacting of the gas blocking inorganic particleswith the compound represented by Formula 1 may be performed byimmersion, i.e., by mixing a composition including the gas blockinginorganic particles, the compound represented by Formula 1, and asolvent at a temperature at about room temperature (e.g., 25° C.) toabout 60° C., and removing the solvent from the resulting mixture.

For example, the reacting of the gas blocking inorganic particles andthe compound represented by Formula 1 may be performed for about 20hours or less, and in an example embodiment, for about 3 hours to about10 hours.

In another embodiment, the reacting of the gas blocking inorganicparticles with the compound represented by Formula 1 may be performed byspraying a composition including the compound represented by Formula 1and a solvent onto the at least one surface of the gas blockinginorganic particles, for example on substantially the entire surface ofeach of the gas blocking inorganic particles.

In the above-described immersion and spray methods, the solvent may beany suitable solvent in which the gas blocking inorganic particles andthe compound represented by Formula 1 may be uniformly mixed ordispersed. For example, the solvent may be at least one selected fromtoluene, methylene chloride, methanol, ethanol, propanol, ethyl acetate,and diethylether.

The washing of the reaction product may be performed using a solvent,for example, acetone. The drying may be performed, for example, at atemperature of about room temperature (e.g., 25° C.) to about 85° C.

Through the above-described processes, the gas blocking inorganicparticles having a hydrophobic coating layer on at least one surfacethereof may be obtained. The gas blocking inorganic particles may havehydrophobic properties. The hydrophobic layer on the gas blockinginorganic particles may be a continuous or non-continuous coating layerand may have a thickness of, for example, about 1 nanometer (nm) toabout 100 nm. Since the thickness of the hydrophobic coating layer isrelatively less than a total thickness of the composite membrane,substantially no reduction in the ion conductivity may occur by applyingthe hydrophobic coating layer on the at least one surface of the gasblocking inorganic particles.

The hydrophobic coating layer may have a thickness of about 1 nm toabout 80 nm, and in another embodiment, about 1 nm to about 50 nm, andin still another embodiment, about 1 nm to about 15 nm. For example, thehydrophobic coating layer may have a thickness of about 1 nm to about 10nm.

In an embodiment, the composite membrane may have a thickness of about10 μm to about 200 μm, for example, about 70 μm to about 100 μm.

A composite membrane according to an embodiment may serve as a lithiumion conductive membrane to protect the anode and as a protectivemembrane which selectively allows lithium ions to pass through toprevent other materials from reacting with the anode. The compositemembrane as a protective layer may be formed as a thin film, thusreducing electrical resistance and improving ion conductivity.

For example, the composite membrane according to an embodiment may beused as a protective layer or an oxygen barrier layer of a lithium airbattery, a protective layer of a lithium-sulfur battery, a protectivelayer, or a separator of an aqueous lithium ion battery, or a separatorof a fuel cell.

The composite membrane according to any embodiment is a membranecomprising polyvinylidene fluoride,N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, lithiumbis(trifluoromethylsulfonyl)imide, SiO₂, andLi_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂ wherein 0<x<2 and 0≤y<3; or amembrane comprising a porous and a layer comprisingpoly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, lithiumbis(trifluoromethanesulfonyl)imide, SiO₂, andLi_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂ wherein 0<x<2 and 0≤y<3 in theporous layer; a membrane comprising polyvinylidene fluoride, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, lithiumbis(trifluoromethylsulfonyl)imide, SiO₂, andLi_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂, wherein 0<x<2, 0≤y<3, having ahydrophobic coating layer on a surface thereof; or a membrane comprisinga porous layer; and a layer comprising poly(diallyldimethylammonium)bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, lithiumbis(trifluoromethanesulfonyl)imide, SiO₂, andLi_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂ wherein 0<x<2 and 0≤y<3, havinga hydrophobic coating layer on a surface thereof on the porous layer.

According to an aspect, a battery assembly includes an electrolyte; alithium metal or a lithium metal alloy; and the composite membrane. Thebattery assembly can be used, for example, for a lithium air battery,lithium sulfur battery, and all solid battery.

According to another aspect of the present disclosure, a lithium airbattery includes a cathode, an anode, and a composite membrane accordingto any of the above-described example embodiments. FIG. 3A is aschematic view illustrating a structure of a lithium air batteryincluding a composite membrane according to an embodiments.

Referring to FIG. 3A, a lithium air battery according to an embodimentmay include an anode electrolyte 34 stacked on an anode 33, a compositemembrane 35 according to an embodiment as a gas blocking layer on theanode electrolyte 34, a cathode 37, and a cathode electrolyte 36 betweenthe composite membrane 35 as a gas blocking layer and the cathode 37.

The anode 33 may be, for example, a lithium metal thin film. Thecomposite membrane 35 may also serve as a lithium metal protectivelayer. The composite membrane 35 according to an embodiment may belightweight and may have improved flexibility and oxygen blockingability.

The electrolyte including the anode electrolyte 34 and the cathodeelectrolyte 36 may be an aqueous electrolyte or non-aqueous electrolyte.These electrolytes may be the same as those to be described later inconnection with a lithium air battery according to another embodiment.

According to another aspect of the present disclosure, a lithium airbattery includes an anode, a composite membrane according to anembodiment, and a cathode including oxygen as a cathode active material.

In an embodiment, the lithium air battery may use an aqueous electrolyteor a non-aqueous electrolyte as an electrolyte between the cathode andthe anode.

When the electrolyte of the lithium air battery is a non-aqueouselectrolyte, the reaction mechanism may be represented by ReactionScheme 1.4Li+O₂→2Li₂O E°=2.91V2Li+O₂→Li₂O₂ E³=3.10V  Reaction Scheme 1

During discharging, lithium from the anode reacts with oxygen from thecathode to form lithium oxide, and oxygen is reduced. On the contrary,during charging, oxygen is oxidized when lithium oxide is reduced.

A shape of the lithium air battery may be any of a variety of suitableshapes, and in an embodiment, the shape may be that of a coin, a button,a sheet, a stack, a cylinder, a plane, or a horn. The lithium airbattery may be applicable as a large battery for electric vehicles.

FIG. 3B is a schematic view illustrating a lithium air battery 40according to another embodiment.

Referring to FIG. 3B, the lithium air battery 40 may have a structure inwhich a composite membrane 45 according to an above-described exampleembodiment is between a cathode 47, which uses oxygen as an activematerial, and an anode 43 on a base 42. An electrolyte 44 may be betweenthe anode 43 and the composite membrane 45. The anode 43, theelectrolyte 44, and the composite membrane 45 may constitute a protectedanode.

The electrolyte 44 may have good lithium ion conductivity and a lowelectrical resistance per unit area against the anode 43.

A lithium ion-conductive solid electrolyte membrane or a separator maybe further included between the anode 43 and the electrolyte 44, orbetween the electrolyte 44 and the composite membrane 45.

The cathode 47 may include a current collector, and a pressing member 49for transferring air to the cathode 47 may be on the current collector.As illustrated in FIG. 3B, the cathode 47 and the anode 43 may beaccommodated in a case 41 made of an insulating resin. Air may besupplied via an air inlet 48 a and may be discharged through an airoutlet 48 b.

As used herein, the term “air” is not limited to atmospheric air, andmay refer to a combination of gases including oxygen, or pure oxygengas.

An electrolyte 46 may be between the composite membrane 45 and thecathode 47. A lithium ion-conductive solid electrolyte membrane or aseparator may be further included between the cathode 47 and theelectrolyte 46, or between the electrolyte 46 and the composite membrane45.

For example, the composite membrane 45 may be on a surface of the anode43 to serve as a protective membrane for protecting lithium of the anode43 from the electrolyte 44.

The composite membrane 45 may be a single layer or a multilayer.

The electrolytes 44 and 46 may be polymer solid electrolytes. Such apolymer solid electrolyte may be a polyethylene oxide doped with alithium salt. For example, the lithium salt may be at least one selectedfrom LiBF₄, LiPF₆, LiSbF₆, LiAsF₆, LiClO₄, LiCF₃SO₃, LiN(SO₂CF₃)₂,LiN(SO₂C₂F₅)₂, LiC(SO₂CF₃)₃, LiN(SO₂F)₂, LiC₄F₉SO₃, and LiAlCl₄.

In another embodiment, the electrolytes 44 and 46 may be liquidelectrolytes including a solvent and a lithium salt.

The solvent may include at least one selected from an aprotic solventand water.

Non-limiting examples of the aprotic solvent are a carbonate-basedsolvent, an ester-based solvent, an ether-based solvent, a ketone-basedsolvent, an amine-based solvent, and a phosphine-based solvent.

Non-limiting examples of the carbonate-based solvent are dimethylcarbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC),dipropyl carbonate (DPC), methylpropyl carbonate (MPC), ethylpropylcarbonate (EPC), ethylene carbonate (EC), propylene carbonate (PC), andbutylene carbonate (BC).

Non-limiting examples of the ester-based solvent are methyl acetate,ethyl acetate, n-propyl acetate, tert-butyl acetate, methyl propionate(MP), ethyl propionate, γ-butyrolactone, decanolide, valerolactone,mevalonolactone, and caprolactone.

Non-limiting examples of the ether-based solvent are dibutyl ether,tetraglyme, diglyme, dimethoxyethane, 2-methyltetrahydrofuran, andtetrahydrofuran. An example of the ketone-based solvent iscyclohexanone.

Non-limiting examples of the amine-based solvent are triethylamine andtriphenylamine. An example of the phosphine-based solvent istriethylphosphine. The embodiments of the present inventive concept arenot limited to the above, and any appropriate aprotic solvent availablein the art may be used.

Examples of the aprotic solvent are nitriles (such as R—CN, wherein R isa C2-C30 linear, branched, or cyclic hydrocarbon-based moiety that mayinclude a double-bond, an aromatic ring, or an ether bond), amides (suchas N,N-dimethylformamide), dioxolanes (such as 1,3-dioxolane), andsulfolanes.

The aprotic solvent may be used alone or in a combination of at leasttwo aprotic solvents. In the latter, a mixing ratio of the at least twoaprotic solvents may be appropriately adjusted depending on a desiredperformance of the battery. This will be understood by one of ordinaryskill in the art.

The electrolytes 44 and 46 may include an ionic liquid.

The electrolytes 44 and 46 may be partially or completely impregnatedinto the anode 43 and the cathode 47, respectively.

In an embodiment, a lithium ion-conductive solid electrolyte membranemay be used as the electrolytes 44 and 46.

The lithium ion-conductive solid electrolyte membrane may include aninorganic material including a lithium ion-conductive glass, a lithiumion-conductive crystal (ceramic or glass-ceramic), or a combinationthereof. For example, the lithium ion-conductive solid electrolytemembrane may include an oxide, in view of chemical stability.

When the lithium ion-conductive solid electrolyte membrane includes alarge amount of lithium ion-conductive crystals, a high ionicconductivity may be attainable. For example, the lithium ion-conductivesolid electrolyte membrane may include an amount of about 50 weightpercent (wt %) or greater, about 55 wt % or greater, or about 60 wt % orgreater, or 50 wt % to 95 wt %, or 55 wt % to 90 wt % of the lithiumion-conductive crystals, based on a total weight of the lithiumion-conductive solid electrolyte membrane.

The lithium ion-conductive crystals may be lithium-ion conductivecrystals having a Perovskite structure, such as Li₃N, LISICON,La_(0.55)Li_(0.35)TiO₃, and the like, LiTi₂P₃O₁₂ crystals having aNASICON structure, or a glass-ceramic able to form these crystals.

For example, the lithium ion-conductive crystals may be Li_(1+x+y)(Al_(q)Ga_(1−g))_(x)(Ti_(h)Ge_(1-h))_(2−x)Si_(y)P_(3−y)O₁₂ crystals(where 0≤q≤1, 0≤h≤1, 0≤x≤1, and 0≤y≤1, and for example, 0≤x≤0.4 and0<y≤0.6, or 0.1≤x≤0.3 and 0.1<y≤0.4). To have a high ionic conductivity,the lithium-ion conductive particles may be substantially free of grainboundaries that may disrupt ionic conduction. For example, a lithiumion-conductive glass-ceramic free of pores or grain boundaries thatimpair the conduction of ions may have high ionic conductivity and highchemical stability.

Non-limiting examples of the lithium ion-conductive glass-ceramic arelithium-aluminum-germanium-phosphate (LAGP),lithium-aluminum-titanium-phosphate (LATP), andlithium-aluminum-titanium-silicon-phosphate (LATSP).

For example, when a parent glass with a composition ofLi₂O—Al₂O₃—TiO₂—SiO₂—P₂O₅ is thermally treated for crystallization, amain crystal phase of Li_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂ (wherein0≤x≤2 and 0≤y≤3) may be obtained. For example, x and y may be asfollows: for example, 0≤x≤0.4 and 0<y≤0.6, and in another embodiment,0.1≤x≤0.3 and 0.1<y≤0.4.

As used herein, the pores or grain boundaries blocking conduction ofions refers to pores or grain boundaries that inhibit conductivity ofthe entire inorganic material including the lithium ion-conductivecrystals to 1/10 or less of conductivity of the lithium ion-conductivecrystals of the inorganic material.

The cathode 47, using oxygen as a cathode active material, may include aconductive material. The conductive material may be porous. Any suitableporous and conductive material may be used as a cathode active material,and in an example embodiment, a porous carbonaceous material may beused. Suitable carbonaceous materials include carbon blacks, graphites,graphenes, activated carbons, carbon fibers, and combinations thereof.The cathode active material may be a metallic conductive material, forexample, a metal fiber, a metal mesh, or the like. For example, thecathode active material may comprise at least one selected from copper,silver, nickel, and aluminum. Organic conductive materials, includingpolyphenylene derivatives, may be used. The above-listed conductivematerials may be used alone or a combination of the conductive materialsmay be used.

The cathode 47 may further include a catalyst for oxidation or reductionof oxygen. Examples of the catalyst include, but are not limited to,precious metal-based catalysts, such as platinum (Pt), gold (Au), silver(Ag), palladium (Pd), ruthenium (Ru), rhodium (Rh), and osmium (Os);oxide-based catalysts, such as manganese oxide, iron oxide, cobaltoxide, and nickel oxide; and organometallic-based catalysts, such ascobalt phthalocyanine. Any appropriate oxidation or reduction catalystfor oxygen, including those available in the art, may be used.

The catalyst may be supported on a support. Examples of the support areoxide, zeolite, a clay-based mineral, and carbon. The oxide may includeat least one oxide of alumina, silica, zirconium oxide, and titaniumdioxide. The oxide may be an oxide bearing at least one metal selectedfrom the group consisting of cerium (Ce), praseodymium (Pr), samarium(Sm), europium (Eu), terbium (Tb), thulium (Tm), ytterbium (Yb),antimony (Sb), bismuth (Bi), vanadium (V), chromium (Cr), manganese(Mn), iron (Fe), cobalt (Co), nickel (Ni), copper (Cu), niobium (Nb),molybdenum (Mo), and tungsten (W). Examples of the carbon available asthe support are, but are not limited to, carbon blacks, such asKETJENBLACK™, acetylene black, channel black, and lamp black; graphites,such as natural graphite, artificial graphite, and expanded graphite;activated carbons; and carbon fibers. Any appropriate material availableas supports, including those in the art, may be used.

The cathode 47 may further include a binder. The binder may include athermoplastic resin or a thermocurable resin. Examples of the binderinclude, but are not limited to, polyethylene, polypropylene,polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVDF),styrene-butadiene rubber, a tetrafluoroethylene-perfluoroalkylvinylethercopolymer, a vinylidene fluoride-hexafluoropropylene copolymer, avinylidene fluoride-chlorotrifluoroethylene copolymer, anethylene-tetrafluoroethylene copolymer, polychlorotrifluoroethylene, afluorovinylidene-pentafluoropropylene copolymer, apropylene-tetrafluoroethylene copolymer, anethylene-chlorotrifluoroethylene copolymer, a vinylidenefluoride-hexafluoropropylene-tetrafluoroethylene copolymer, a vinylidenefluoride-perfluoromethylvinylether-tetrafluoro ethylene copolymer, andan ethylene-acrylic acid copolymer, which may be used alone or in anycombination thereof. Any suitable appropriate binder, including thoseavailable in the art, may be used.

The cathode 47 may be manufactured as follows. For example, an oxygenoxidation/reduction catalyst, a conductive material, and a binder may bemixed together, and the resultant mixture may be added to an appropriatesolvent to prepare a cathode slurry. The cathode slurry may be coated ona surface of a current collector and then dried, optionally followed bypress-molding to improve electrode density, to thereby form a cathode.Optionally the cathode may include a lithium oxide. Optionally theoxygen oxidation/reduction catalyst may be omitted.

A porous body in a matrix or mesh form may be used as the currentcollector to facilitate diffusion of oxygen. A porous metal plate madeof, for example, stainless steel, nickel, or aluminum may be used.Materials for the current collector are not particularly limited, andany appropriate material for current collectors available in the art maybe used. The current collector may be coated with an anti-oxidationmetal or an alloy coating layer to prevent oxidation.

In an embodiment, when the anode 43 of the lithium air battery is alithium-containing anode, the lithium-containing anode may include alithium metal, a lithium metal-based alloy, a material that allowsintercalation and deintercalation of lithium, or a material that allowsdeposition and dissolution of lithium. Materials for the anode 43 arenot particularly limited to these materials, and any suitable material,including those available in the art, that includes Li or allowsintercalation and deintercalation of lithium, or any suitable material,including those available in the art, that allows deposition anddissolution of lithium may be used. The cathode may determine a capacityof the lithium air battery.

For example, the anode 43 may be a lithium metal. Examples of thelithium-based alloy include alloys with at least one selected fromaluminum (Al), tin (Sn), magnesium (Mg), indium (In), calcium (Ca),titanium (Ti), and vanadium (V).

A separator may be disposed between the cathode 47 and the anode 43. Theseparator is not specifically limited, and may have any compositiondurable in an operational environment of the lithium air battery. Forexample, the separator may be a polymeric non-woven fabric, such aspolypropylene-based non-woven fabric or polyphenylene sulfide-basednon-woven fabric, or a porous film of an olefin-based polymer, such aspolypropylene or polyethylene; a combination of at least two of thesematerials may be used to form the separator.

According to an embodiment, the lithium air battery may include acomposite membrane according to any one of the above-describedembodiments and thus have improved specific capacity and lifetimecharacteristics.

For example, the separator between the cathode and the anode may be amixed multi-layer such as a two-layered polyethylene/polypropyleneseparator, a three-layered polyethylene/polypropylene/polyethyleneseparator, or a three-layered polypropylene/polyethylene/polypropyleneseparator.

As noted above, the concentration of the lithium salt in the liquidelectrolyte may be about 0.01M to about 5M, and in some other exampleembodiments, about 0.1M to about 2M.

Substituents in the formulae above may be defined as follows.

As used herein, the term “alkyl” indicates a completely saturated,branched or unbranched (or a straight or linear) hydrocarbon group.

Non-limiting examples of the “alkyl” group include methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, t-butyl, isopentyl,neopentyl, n-hexyl, 3-methylhexyl, 2,2-dimethylpentyl,2,3-dimethylpentyl, and n-heptyl.

At least one hydrogen atom of the alkyl group may be substituted with ahalogen atom, a C1-C20 alkyl group substituted with a halogen atom (forexample, CCF₃, CF₃, CHCF₂, CHF₂, CH₂F, CCl₃, a C1-C20 alkoxy group, aC2-C20 alkoxyalkyl group, a hydroxyl group, a nitro group, a cyanogroup, an amino group, an amidino group, a hydrazine group, a hydrazonegroup, a carboxyl group or a salt thereof, a sulfonyl group, a sulfamoylgroup, a sulfonic acid group or a salt thereof, a phosphoric acid groupor a salt thereof, a C1-C20 alkyl group, a C2-C20 alkenyl group, aC2-C20 alkynyl group, a C1-C20 heteroalkyl group, a C6-C20 aryl group, aC7-C20 arylalkyl group, a C6-C20 heteroaryl group, a C7-C20heteroarylalkyl group, a C6-C20 heteroaryloxy group, a C7-C20heteroaryloxyalkyl group, or a C7-C20 heteroarylalkyl group.

The term “halogen atom” indicates fluorine, bromine, chlorine, iodine.

The term “C1-C20 alkyl group substituted with a halogen atom” indicatesa C1-C20 alkyl group substituted with at least one halo group.Non-limiting examples of the C1-C20 alkyl group substituted with ahalogen atom include monohaloalkyl, polyhaloalkyls includingdihaloalkyl, or perhaloalkyl.

Monohaloalkyls indicate alkyl groups including one iodine, bromine,chloride, or fluorine atom. Dihaloalkyls and polyhaloalkyls indicatealkyl groups including at least two identical or different halo atoms.

As used herein, the term “alkoxy” represents “alkyl-O—”, wherein thealkyl is the same as described above. Non-limiting examples of thealkoxy group include methoxy, ethoxy, propoxy, 2-propoxy, butoxy,t-butoxy, pentyloxy, and hexyloxy. At least one hydrogen atom of thealkoxy group may be substituted with any of the substituents recitedabove that may be substituted in place of at least one hydrogen atom ofthe alkyl group.

As used herein, the term “alkenyl” indicates a branched or unbranchedhydrocarbon group with at least one carbon-carbon double bond.Non-limiting examples of the alkenyl group include vinyl, allyl,butenyl, propenyl, and isobutenyl. At least one hydrogen atom in thealkenyl group may be substituted with any of the substituents recitedabove that may be substituted in place of at least one hydrogen atom ofthe alkyl group.

As used herein, the term “alkynyl” indicates a branched or unbranchedhydrocarbon group with at least one carbon-carbon triple bond.Non-limiting examples of the “alkynyl” group include ethynyl, butynyl,isobutynyl, isopropynyl, and propynyl.

At least one hydrogen atom of the “alkynyl” group may be substitutedwith any of the substituents recited above that may be substituted inplace of at least one hydrogen atom of the alkyl group.

The term “aliphatic group” means a saturated or unsaturated linear orbranched hydrocarbon group. An aliphatic group may be an alkyl, alkenyl,or alkynyl group, for example.

“Alkylene” means a straight, branched or cyclic divalent aliphatichydrocarbon group, and may have from 1 to about 18 carbon atoms, morespecifically 2 to about 12 carbons. Exemplary alkylene groups includemethylene (—CH₂—), ethylene (—CH₂CH₂—), or propylene (—(CH₂)₃—).

As used herein, the term “aryl” group, which is used alone or incombination, indicates an aromatic hydrocarbon group containing at leastone ring.

“Arylene” means a divalent radical formed by the removal of two hydrogenatoms from one or more rings of an aromatic hydrocarbon, wherein thehydrogen atoms may be removed from the same or different rings(preferably different rings), each of which rings may be aromatic ornonaromatic.

The term “aryl” is construed as including a group with an aromatic ringfused to at least one cycloalkyl ring.

Non-limiting examples of the “aryl” group include phenyl, naphthyl, andtetrahydronaphthyl.

At least one hydrogen atom of the “aryl” group may be substituted withany of the substituents recited above that may be substituted in placeof at least one hydrogen atom of the alkyl group.

The term “arylalkyl” indicates an alkyl group in which one of thehydrogens is substituted with an aryl group. Examples of the arylalkylgroup are benzyl groups.

As used herein, the term “aryloxy” indicates “—O-aryl”. An example ofthe aryloxy group is phenoxy. At least one hydrogen atom of the“aryloxy” group may be substituted with any of the substituents recitedabove that may be substituted in place of at least one hydrogen atom ofthe alkyl group.

As used herein, the term “heteroaryl group” indicates a monocyclic orbicyclic organic aromatic group including at least one heteroatomselected from among nitrogen (N), oxygen (O), phosphorous (P), andsulfur (S), wherein the rest of the cyclic atoms are all carbon. Theheteroaryl group may include, for example, one to five heteroatoms, andin another embodiment, may include a five- to ten-membered ring. In theheteroaryl group, S or N may be present in various oxidized forms.

At least one hydrogen atom of the “heteroaryl” group may be substitutedwith any of the substituents recited above that may be substituted inplace of at least one hydrogen atom of the alkyl group.

“Heteroarylene” means a divalent radical formed by the removal of twohydrogen atoms from one or more rings of a heteroaryl moiety, whereinthe hydrogen atoms may be removed from the same or different rings(preferably the same ring), each of which rings may be aromatic ornonaromatic.

The term “heteroarylalkyl” group indicates an alkyl group substitutedwith a heteroaryl group. At least one hydrogen atom of theheteroarylalkyl group may be substituted with any of the substituentsrecited above that may be substituted in place of at least one hydrogenatom of the alkyl group.

The term “heteroaryloxy” group indicates a “—O-heteroaryl moiety”. Atleast one hydrogen atom of the heteroaryloxy group may be substitutedwith any of the substituents that are the same as those recited above inconjunction with the alkyl group.

The term “heteroaryloxyalkyl” group indicates an alkyl group substitutedwith a heteroaryloxy group. At least one hydrogen atom of theheteroaryloxyalkyl group may be substituted with any of the substituentsrecited above that may be substituted in place of at least one hydrogenatom of the alkyl group.

As used herein, the term “carbocyclic” group indicates a saturated orpartially unsaturated non-aromatic monocyclic, bicyclic, or tricyclichydrocarbon group.

Non-limiting examples of the monocyclic hydrocarbon group includecyclopentyl, cyclopentenyl, cyclohexyl, and cyclohexcenyl. Non-limitingexamples of the bicyclic hydrocarbon group include bornyl,decahydronaphthyl, bicyclo[2.1.1]hexyl, bicyclo[2.2.1]heptyl,bicyclo[2.2.1]heptenyl, or bicyclo[2.2.2]octyl.

An example of the tricyclic hydrocarbon group is adamantyl.

At least one hydrogen atom of the “carbocyclic group” may be substitutedwith any of the substituents recited above that may be substituted inplace of at least one hydrogen atom of the alkyl group.

As used herein, the term “heterocyclic group” indicates a five- toten-membered cyclic group including at least one heteroatom such as N,S, P, or O. An example of the heterocyclic group is pyridyl. At leastone hydrogen atom in the heterocyclic group may be substituted with anyof the substituents recited above that may be substituted in place of atleast one hydrogen atom of the alkyl group.

The term “sulfonyl” indicates R″—SO₂—, wherein R″ is a hydrogen atom,alkyl, aryl, heteroaryl, aryl-alkyl, heteroaryl-alkyl, alkoxy, aryloxy,cycloalkyl, or a heterocyclic group.

The term “sulfamoyl group” refers to H₂NS(O₂)—, alkyl-NHS(O₂)—,(alkyl)₂NS(O₂)—, aryl-NHS(O₂)—, alkyl(aryl)-NS(O₂)—, (aryl)₂NS(O)₂,heteroaryl-NHS(O₂)—, (aryl-alkyl)-NHS(O₂)—, or(heteroaryl-alkyl)-NHS(O₂)—.

At least one hydrogen atom of the sulfamoyl group may be substitutedwith any of the substituents recited above that may be substituted inplace of at least one hydrogen atom of the alkyl group.

The term “amino group” indicates a group with a nitrogen atom covalentlybonded to at least one carbon or heteroatom. “Amino” has the generalformula —N(R)₂, wherein each R is independently hydrogen, a C1 to C6alkyl, or a C6 to C12 aryl. The amino group may include, for example,—NH₂ and substituted moieties. The term “amino group” also refers to an“alkylamino group” with nitrogen bonded to at least one additional alkylgroup, and “arylamino” and “diarylamino” groups with nitrogen bonded toone or two aryl groups, respectively.

One or more embodiments of the present disclosure will now be describedin detail with reference to the following examples. However, theseexamples are only for illustrative purposes and are not intended tolimit the scope of the one or more embodiments of the presentdisclosure.

EXAMPLES Preparation Example 1

PFO—SH-LTAP, which refers to the reaction product of1H,1H,2H,2H-perfluorooctyltriethoxysilane (PFO),3-(mercaptopropyl)trimethoxysilane (SH), andLi_(1.4)Ti_(1.6)Al_(0.4)P₃O₁₂(LTAP), as a surface-modified LTAP wasprepared using PFO and 3-(mercaptopropyl)trimethoxysilane (SH) by thefollowing processes.

A lithium ion-conductive ceramic plate (Ohara glass, available fromOhara corporation, thickness of about 260 μm) including crystalline LTAP(L_(1.4)Ti_(1.6)Al_(0.4)P₃O₁₂) was ground and then sieved to obtain LTAPparticles having a size (average particle diameter) of about 49 μm.

About 200 mg of the LTAP particles, 20 mL of toluene, and 50 mg of(3-mercaptopropyl)trimethoxysilane (SH) were added into a vial andstirred at about 25° C. for about 7 hours.

The resulting reaction product was filtered, washed with acetone, andthen vacuum dried at about 60° C. for about 2 hours. The vacuum-driedproduct was sieved to obtain SH-LTAP particles having a size (averageparticle diameter) of about 49 μm, which are LTAP particles having ahydrophobic coating layer resulting from condensation of SH.

About 200 mg of the SH-LTAP particles, 20 mg of toluene, and about 50 gof PFO were mixed together for about 30 minutes. The reaction mixturewas filtered, washed with acetone, vacuum-dried at about 60° C. forabout 2 hours, and then sieved to obtain PFO—SH-LTAP particles modifiedwith PFO.

The PFO—SH-LTAP particles had a uniform hydrophobic coating layermodified with PFO and SH.

Example 1

Polyvinylidene fluoride, DEME(N,N-diethyl-N-methyl-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide), and Li(CF₃SO₂)₂N (LiTFSI) weremixed in a weight ratio of 1:1:1 in 100 mL of N-methylpyrrolidone (NMP).About 5 parts by weight of SiO₂ particles as inorganic particles havinga particle diameter of about 7 nm, based on 100 parts by weight of DEME,were added thereto and stirred for about 20 minutes to prepare amixture.

This mixture was cast onto a glass substrate using a doctor blade, andabout 5 mg (per unit area) of PFO—SH-LTAP particles (average particlediameter: 30 μm) were applied thereto, thereby preparing a compositemembrane having a thickness of about 60 μm.

Example 2

Polyvinylidene fluoride, DEME(N,N-diethyl-N-methyl-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide), and LiTFSI were mixed in a weightratio of 1:1:1 in 100 mL of NMP. About 5 parts by weight of SiO₂particles as inorganic particles having a particle diameter of about 7nm, based on 100 parts by weight of DEME, were added thereto and stirredfor about 20 minutes to prepare a mixture.

The resultant mixture was cast onto a glass substrate using a doctorblade, and about 5 mg (per unit area) of the PFO—SH-LTAP particles(average particle diameter: 30 μm) of Preparation Example 1 were appliedthereto, thereby preparing a composite membrane having a thickness ofabout 60 μm.

Example 3

Poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (TFSI),DEME (N,N-diethyl-N-methyl-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide), and LiTFSI were mixed in a weightratio of 1:1:1 in 100 mL of NMP. About 5 parts by weight of SiO₂particles as inorganic particles having a particle diameter of about 7nm, based on 100 parts by weight of DEME, were added thereto and stirredfor about 20 minutes to prepare a mixture.

This mixture was cast onto a porous separator (PE/PP membrane), and thePFO—SH-LTAP particles (average particle diameter: 30 μm) of PreparationExample 1 were applied thereto, thereby preparing a composite membrane.Here, the amount of the PFO—SH-LTAP particles was about 5 mg per unitarea of the composite membrane.

Example 4

1.38 g of polyethylene oxide powder (having a weight average molecularweight of about 100,000 Da, available from Aldrich) and 0.9 g ofLi(CF₃SO₂)₂N (LiTFSI, Wako) were dispersed in 100 mL of acetonitrile(AN) used as a solvent, and stirred for about 24 hours to prepare anelectrolyte forming composition.

This electrolyte forming composition was cast onto a Teflon dish, driedat about 20° C. for about 24 hours to remove the acetonitrile solvent,and then vacuum-dried at about 60° C. for about 12 hours to obtain aPEO₁₀LiTFSI polymer electrolyte (hereinafter, referred to as PEO polymerelectrolyte). The PEO polymer electrolyte had an average thickness ofabout 60 μm.

A lithium metal was disposed on a surface of the PEO polymer electrolyte(having a weight average molecular weight of about 1×10⁵ Da), and thecomposite membrane of Example 1 was stacked on the opposite surface ofthe PEO polymer electrolyte. Next, another PEO polymer electrolyte wasstacked on the composite membrane of Example 1, thereby manufacturing abattery assembly (lithium metal/PEO polymer electrolyte/PVA-LTAPcomposite membrane/PEO polymer electrolyte/lithium metal).

Examples 5 and 6

Battery assemblies were manufactured in the same manner as in Example 4,except that the composite membranes of Examples 2 and 3 were usedrespectively for Examples 5 and 6 instead of the composite membrane ofExample 1.

Example 7

First, a cathode in sheet form was formed using a mixture of multiwalledcarbon nanotubes (available from XinNano Material, Inc.), DEME-TFSI(N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide) containing 1 M lithiumbis(trifluoromethyl sulfonylimide) (LiTFSI), and polyvinylidene fluoridein a weight ratio of about 5:25:1. The cathode in sheet form was cutinto a disc form having a diameter of about 8 mm.

A lithium metal (having a thickness of 500 μm) in disc form having adiameter of about 15 mm was used as an anode.

2 g of polyethylene oxide, 0.31 g of silica gel, and 0.26 g of LiTFSIwere dissolved in 50 mL of acetonitrile and mixed for about 7 hours toobtain a polymer solution. This polymer solution was cast onto a Teflondish and dried to obtain a polymer electrolyte film having a thicknessof about 190 μm. This polymer electrolyte film was punched into apolymer electrolyte disc having a diameter of about 15 mm.

A copper thin film, the lithium metal disc, the polymer electrolytedisc, the composition membrane of Example 2, a cathode, and a gasdiffusion layer (35BA, available from SGL Group) were assembled tomanufacture a lithium air battery.

Comparative Example 1

Polyvinylidene fluoride (PVDF), DEME(N,N-diethyl-N-methyl-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide), and LiTFSI were mixed in a weightratio of about 1:1:1 in 100 mL of NMP to obtain a mixture.

This mixture was cast onto a glass substrate using a doctor blade anddried to prepare an ion-conductive layer having a thickness of about 40μm.

Comparative Example 2

Poly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide (TFSI),DEME (N,N-diethyl-N-methyl-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide), and LiTFSI were mixed in a weightratio of 1:1:1 in 100 mL of NMP. About 5 parts by weight of SiO₂particles as inorganic particles having a particle diameter of about 7nm, based on 100 parts by weight of DEME, were added thereto and stirredfor about 20 minutes to prepare a mixture.

This mixture was cast onto a porous separator (PE/PP membrane) and driedto prepare a membrane.

Comparative Example 3

A LTAP membrane (Ohara glass, available from Ohara corporation) having athickness of about 260 μm was used.

Comparative Example 4

Polyvinylidene fluoride, DEME (N,N-diethyl-N-methyl-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide), and LiTFSI were mixed in a weightratio of 1:1:1 in 100 mL of N-methylpyrrolidone. LTAP particles (averageparticle diameter: 30 μm) and SiO₂ particles as inorganic particleshaving a particle diameter of about 7 nm were added thereto and stirredfor about 20 minutes to prepare a mixture. The amount of the LTAPparticles was 300 parts by weight, and the amount of the SiO₂ particleswas 0.05 parts by weight, each based on 100 parts by weight of DEME.

The mixture was cast onto a glass substrate using a doctor blade, andLTAP particles (average particle diameter: 30 μm) were added thereto,thereby preparing a composite membrane having a thickness of about 60μm. Here, the amount of LTAP particles was about 5 mg per unit area ofthe composite membrane.

Comparative Examples 5 and 6

Battery assemblies were manufactured in the same manner as in Example 4,except that the composite membranes of Comparative Examples 1 and 2 wererespectively used for Comparative Examples 5 and 6 instead of thecomposite membrane of Example 1.

Comparative Example 7

An electrode assembly was manufactured in the same manner as in Example7, except that the composite membrane of Comparative Example 1 was usedinstead of the composite membrane of Example 2.

Evaluation Example 1: Scanning Electron Microscopic (SEM) Analysis

The composite membrane of Example 2 was analyzed using a scanningelectron microscope system (SNE-4500M/MCM-100, available from SEC Co.,Ltd.).

The SEM analysis results of the top and bottom surfaces of the compositemembrane of Example 2 are shown in FIGS. 5A and 5B, respectively. Thestructure of the composite membrane 50 of Example 2 is shown in FIG. 4A.The SEM analysis results of the top and bottom surfaces of the compositemembrane of Comparative Example 4 are shown in FIGS. 5C and 5D,respectively. FIG. 4B is a schematic cross-sectional view illustrating astructure of a membrane 50 of Comparative Example 4 as a gas blockingmembrane;

Referring to FIGS. 4A, 5A, and 5B the composite membrane of Example 2was found to have a structure of gas blocking inorganic particles 51non-continuously aligned on a surface (first surface) adjacent to acathode (not shown), unlike the composite membrane of ComparativeExample 4 in FIGS. 4B, 5C, and 5D. In other words, LTAP particles as gasblocking inorganic particles 51 of the composite membrane of Example 2were aligned in a region away from a lithium anode to inhibit reactionwith lithium of the lithium anode.

As depicted in FIG. 4A, the gas blocking inorganic particles 51 of thecomposite membrane 50 of Example 2 were found to be alignednon-continuously, as exemplified by a spacing between adjacent gasblocking inorganic particles 51 as shown in FIG. 4A. This non-continuousalignment of the gas blocking inorganic particles in the compositemembrane of Example 2 may prevent resistance of gas blocking inorganicparticles to migration 52 of lithium ions. In contrast, as depicted inFIG. 4B, and while not wanting to be bound by theory, resistance againstmigration of lithium ions may likely occur when the gas blockinginorganic particles 51 have a continuous alignment, e.g., contact, orform an agglomerate 56 which blocks the migration path 54 of lithiumions. Therefore, the composite membrane of Example 2 may have improvedion conductivity as compared with the continuously aligned gas blockingparticles 51 as illustrated in FIG. 4B.

Evaluation Example 2: Resistance Characteristics

Membrane assemblies were manufactured by sputtering platinum againstopposite surfaces of each of the composite membranes of Examples 1 and 2and the LTAP membrane of Comparative Example 4. The results ofresistance measurement of the battery assemblies are shown in Table 1.

TABLE 1 Resistivity Resistance per area Example Composition (Ω · cm) (Ω· cm⁻²) Example 1 PVDF, LTAP 4.28E+05 1.93E+03 Example 2 PVDF,PFO-SH-LTAP 4.62E+05 4.62E+03 Comparative PVDF + LTAP blend 7.04E+082.11E+06 Example 4

Referring to Table 1, the composite membrane of Examples 1 and 2 wasfound to have reduced resistivity and resistance per area, compared withthe membrane of Comparative Example 4.

Evaluation Example 3: Weight and Radius of Curvature of Membrane

A weight and a radius of curvature of each of the composite membranes ofExamples 1 to 3 and the membranes of Comparative Examples 1 to 3 wereevaluated according to the following method.

The radius of curvature was measured as a radius of a circle formed bybending a membrane, using a cylindrical mandrel bend tester (availablefrom Sheen Instruments) to bend each membrane according to ISO 1519, andby positive bending in this test.

The results of the radius of curvature measurements are shown in Table2.

TABLE 2 Example Weight (mg/cm²) Radius of curvature (mm) Example 1 10.22 Example 2 7.3 2 Example 3 6.4 2 Comparative Example 1 3.1 2Comparative Example 2 3.7 2 Comparative Example 3 88 >32

Referring to FIG. 2 , the composite membranes of Examples 1 to 3 werefound to have good flexibility.

Evaluation Example 4: Resistance 1) Examples 4 and 5 and ComparativeExample 5

Resistance characteristics of the battery assemblies of Examples 4 and 5and Comparative Example 5 were evaluated. The results are shown in FIG.6A.

Referring to FIG. 6A, the battery assemblies of Examples 4 and 5 werefound to have improved resistance characteristics as compared with thebattery assembly of Comparative Example 5.

2) Example 6 and Comparative Example 6

Resistance characteristics of the battery assemblies of Example 6 andComparative Example 6 were evaluated. The results are shown in FIG. 6B.

Referring to FIG. 6B, the battery assembly of Example 6 was found tohave improved resistance characteristics as compared with the batteryassembly of Comparative Example 6.

Evaluation Example 4: Oxygen Permeability Analysis 1) Examples 1 and 2and Comparative Example 1

Oxygen permeability of each of the composite membranes of Examples 1 and2 and the ion conductive layer of Comparative Example 1 were evaluatedaccording to the following method.

Sample discs each having an area of 1 cm² was used for an oxygenpermeation test using an oxygen transmission rate tester (OX-TRAN 2/21ML, available from MOCON Inc.).

As a result of the oxygen permeation test, the composite membranes ofExamples 1 and 2 were found to have improved oxygen blockingcharacteristics as compared with the ion conductive layer of ComparativeExample 1.

Evaluation Example 5: Cycle Characteristics of Lithium Air Battery

The lithium air batteries of Example 7 and Comparative Example 7 wereplaced in a chamber at about 60° C. in an oxygen atmosphere. Eachlithium air battery was discharged in a constant current (CC) mode (0.24milliamperes per square centimeter (mA/cm²)) at an oxygen pressure of 1atm and charged in a constant voltage (CV) mode (4.3 V).

A charge-discharge capacity of each of the lithium air batteries was setto about 200 milliampere hours per gram of carbon (mAh/g_(carbon)) Cyclecharacteristics of the lithium air batteries were evaluated.

As a result, the lithium air battery of Example 7 was found to haveimproved cycle characteristics as compared with the lithium air batteryof Comparative Example 7.

As described above, according to the one or more example embodiments, acomposite membrane including a non-continuously aligned structure of gasblocking inorganic particles in an ion-conductive polymer layer may haveimproved ion conductivity, flexibility, and gas blocking ability, andmay be formed with a large size. A lithium air battery having improvedcell performance may be manufactured by using the composite membrane.

It should be understood that example embodiments described herein shouldbe considered in a descriptive sense only and not for purposes oflimitation. Descriptions of features or aspects within each exampleembodiment should typically be considered as available for other similarfeatures or aspects in other embodiments.

While one or more example embodiments have been described with referenceto the figures, it will be understood by those of ordinary skill in theart that various changes in form and details may be made therein withoutdeparting from the spirit and scope as defined by the following claims.

What is claimed is:
 1. A composite membrane comprising: anion-conductive polymer layer having a first surface and an oppositesecond surface; a plurality of gas blocking inorganic particlesnon-continuously aligned as a single monolayer in a substantiallyhorizontal direction and disposed on the first or the second surface ofthe ion-conductive polymer layer, or a plurality of gas blockinginorganic particles as a single monolayer within the ion-conductivepolymer, wherein the plurality of the non-continuously aligned particlesdisposed on the first or the second surface, and the plurality ofparticles within the ion-conductive polymer, do not extend from thefirst surface to the opposite second surface of the ion-conductivepolymer layer; and wherein the composite membrane has a radius ofcurvature of about 10 millimeters or less.
 2. The composite membrane ofclaim 1, wherein the radius of curvature is about 2 millimeters to about5 millimeters.
 3. The composite membrane of claim 1, wherein thecomposite membrane further comprises a porous layer.
 4. The compositemembrane of claim 1, wherein the particles within the ion-conductivepolymer layer do not contact the first and the opposite second surfaceof the ion-conductive polymer layer.
 5. The composite membrane of claim1, wherein the plurality of aligned particles, or the plurality ofparticles within the ion-conductive polymer, have an average particlediameter of about 1 micrometer to about 300 micrometers, and theplurality of aligned particles disposed on the composite membrane occupyabout 70% or greater of a total area of the composite membrane.
 6. Thecomposite membrane of claim 1, wherein the plurality of alignedparticles disposed on the first or the second surface of theion-conductive polymer layer, or the plurality of particles within theion-conductive polymer layer, comprise at least one of a glassy activemetal ionic conductor, an amorphous active metal ionic conductor, aceramic active metal ionic conductor, or a glass-ceramic active metalionic conductor.
 7. The composite membrane of claim 1, wherein the totalamount of the plurality of aligned particles, or the plurality ofparticles within the ion-conductive polymer, is from about 10 parts toabout 90 parts by weight, based on 100 parts by weight of a total weightof the composite membrane, and wherein the plurality of alignedparticles disposed on the surface of the composite membrane occupy about70% or greater of a total area of the surface of the composite membrane.8. The composite membrane of claim 1, wherein the plurality of alignedparticles, or the plurality of particles within the ion-conductivepolymer, comprise at least one ofLi_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂ wherein 0<x<2 and 0≤y<3,BaTiO₃, Pb(Zr_(r)Ti_(1−r))O₃ wherein 0≤r≤1,Pb_(1−x)La_(x)Zr_(1−y)Ti_(y)O₃ wherein 0≤x<1 and 0≤y<1,Pb(Mg₃Nb_(2/3))O₃—PbTiO₃ (PMN-PT), HfO₂, SrTiO₃, SnO₂, CeO₂, Na₂O, MgO,NiO, CaO, BaO, ZnO, ZrO₂, Y₂O₃, Al₂O₃, TiO₂, SiO₂, SiC, Li₃PO₄,Li_(x)Ti_(y)(PO₄)₃, wherein 0<x<2 and 0<y<3, Li_(x)Al_(y)Ti_(z)(PO₄)₃,wherein 0<x<2 and 0<y<1 and 0<z<3,Li_(1+x+y)(Al_(q)Ga_(1−q))_(x)(Ti_(h)Ge_(1−h))_(2−x)Si_(y)P_(3−y)O₁₂wherein 0≤q≤1 and 0≤h≤1 and 0≤x≤1 and 0≤y≤1, Li_(x)La_(y)TiO₃ wherein0<x<2 and 0<y<3, Li_(x)Ge_(y)P_(z)S_(w) wherein 0<x<4 and 0<y<1 and0<z<1 and 0<w<5, Li_(x)N_(y) wherein 0<x<4 and 0<y<2, Li_(x)Si_(y)S_(z)wherein 0≤x<3 and 0<y<2 and 0<z<4, Li_(x)P_(y)S_(z) wherein 0≤x<3 and0<y<3 and 0<z<7, Li₂O, LiF, LiOH, Li₂CO₃, LiAlO₂,Li₂O—Al₂O₃—SiO₂—P₂O₅—TiO₂—GeO₂, or Li_(3+x)La₃M₂O₁₂ wherein M is Te, Nb,or Zr, and x is an integer from 1 to
 10. 9. The composite membrane ofclaim 1, wherein the ion-conductive polymer layer comprises at least oneof polyethylene oxide, polyvinylidene fluoride, polyvinylpyrrolidone,polyvinyl alcohol, poly 2-vinylpyridine, polytetrafluoroethylene, atetrafluoroethylene-hexafluoropropylene copolymer,polychlorotrifluoroethylene, a perfluoroalkoxy copolymer, a fluorinatedcyclic ether, polyethylene oxide diacrylate, polyethylene oxidedimethacrylate, polypropylene oxide diacrylate, polypropylene oxidedimethacrylate, polymethyleneoxide diacrylate, polymethyleneoxidedimethacrylate, poly(C1-C4 alkyl)diol diacrylate, poly(C1-C4 alkyl)dioldimethacrylate, polydivinylbenzene, polyether, polycarbonate, polyamide,polyester, polyvinyl chloride, polyimide, polycarboxylic acid,polysulfonic acid, polysulfone, polystyrene, polyethylene,polypropylene, poly(p-phenylene), polyacetylene, poly(p-phenylenevinylene), polyaniline, polypyrrole, polythiophene, polyacene,poly(naphthalene-2,6-diyl), polypropylene oxide, a vinylidenefluoride-hexafluoropropylene copolymer, poly(vinyl acetate), poly(vinylbutyral-co-vinyl alcohol-co-vinyl acetate), poly(methylmethacrylate-co-ethyl acrylate), polyacrylonitrile, poly(vinylchloride-co-vinyl acetate), poly(1-vinyl pyrrolidone-co-vinyl acetate),polyacrylate, polymethacrylate, polyurethane, polyvinyl ether, anacrylonitrile-butadiene rubber, a styrene-butadiene rubber, anacrylonitrile-butadiene-styrene rubber, a sulfonatedstyrene/ethylene-butylene triblock copolymer, epoxide resin, and apolymer obtained from at least one acrylate monomer selected fromethoxylated neopentyl glycol diacrylate, ethoxylated bisphenol Adiacrylate, a C10-C30 alkyl acrylate, ethoxylated aliphatic urethaneacrylate, or ethoxylated (C1-C20 alkyl)phenol acrylate.
 10. Thecomposite membrane of claim 1, wherein the ion-conductive polymercomprises polyvinylidene fluoride,N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, and lithiumbis(trifluoromethylsulfonyl)imide, and the plurality of alignedparticles, or the plurality of particles within the ion-conductivepolymer, comprises SiO₂, and Li_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂wherein 0<x<2 and 0≤y<3; or the composite membrane further comprises aporous layer, the ion conductive layer comprisespoly(diallyldimethylammonium) bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, lithiumbis(trifluoromethanesulfonyl)imide, and plurality of aligned particles,or the plurality of particles within the ion-conductive polymer,comprises SiO₂, and Li_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂ wherein0<x<2 and 0≤y<3, wherein the ion-conductive polymer and the plurality ofaligned particles are disposed on the porous layer; or theion-conducting polymer comprises polyvinylidene fluoride, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, and lithiumbis(trifluoromethylsulfonyl)imide, and the plurality of alignedparticles, or the plurality of particles within the ion-conductivepolymer, comprises SiO₂, and Li_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂,wherein 0<x<2, 0≤y<3, and at least a portion of the aligned particles,and the plurality of particles within the ion-conductive polymer,include a hydrophobic coating layer on a surface; or the compositemembrane further comprises a porous layer; the ion-conductive layercomprises poly(diallyldimethylammonium)bis(trifluoromethanesulfonyl)imide, N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, and lithiumbis(trifluoromethanesulfonyl)imide, and the plurality of alignedparticles, and the plurality of particles within the ion-conductivepolymer, comprise SiO₂, and Li_(1+x+y)Al_(x)Ti_(2−x)Si_(y)P_(3−y)O₁₂,wherein 0<x<2 and 0≤y<3, and at least a portion of the alignedparticles, or the plurality of particles within the ion-conductivepolymer, include a hydrophobic coating layer on a surface on the porouslayer.
 11. The composite membrane of claim 1, further comprising atleast one of an ionic liquid, a lithium salt, and a polymeric ionicliquid.
 12. The composite membrane of claim 11, wherein the lithium saltcomprises at least one of LiPF₆, LiBF₄, LiSbF₆, LiAsF₆, LiN(SO₂C₂F₅)₂,Li(CF₃SO₂)₂N, Li(FSO₂)₂N, LiC₄F₉SO₃, LiClO₄, LiAlO₂, LiAlCl₄,LiN(C_(x)F_(2x+1)SO₂)(C_(y)F_(2+y)SO₂) wherein x and y are positiveintegers, LiF, LiBr, LiCl, LiOH, LiI, or LiB(C₂O₄)₂, wherein the ionicliquid comprises at least one of N,N-diethyl-N-methyl-N-(2-methoxyethyl)ammoniumbis(trifluoromethanesulfonyl)imide, N-methyl-N-propylpyrrolidiniumbis(trifluoromethanesulfonyl)imide, N-butyl-N-methylpyrrolidiniumbis(3-trifluoromethanesulfonyl)imide, 1-butyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide, or 1-ethyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide, and wherein the polymeric ionicliquid comprises at least one of poly(diallyldimethylammonium)trifluoromethanesulfonylimide, poly(1-methacryloyloxypropyl-3-methylimidazolium) bis(trifluoromethanesulfonesulfonyl imide),or poly(1-vinyl-3-ethylimidazolium) bis(trifluoromethanesulfonesulfonylimide).
 13. The composite membrane of claim 1, wherein the alignedparticles, or the plurality of particles within the ion-conductivepolymer, include a hydrophobic coating layer on a surface.
 14. Thecomposite membrane of claim 13, wherein the hydrophobic coating layercomprises a condensation reaction product of at least one compoundrepresented by Formula 1:

wherein, in Formula 1, R₁ to R₃ are each independently selected from asubstituted or unsubstituted C1-C20 alkyl group, a substituted orunsubstituted C1-C20 alkoxy group, a substituted or unsubstituted C2-C20alkenyl group, a substituted or unsubstituted C2-C20 alkynyl group, asubstituted or unsubstituted C6-C20 aryl group, a substituted orunsubstituted C7-C20 arylalkyl group, a substituted or unsubstitutedC6-C20 aryloxy group, a substituted or unsubstituted C2-C20 heteroarylgroup, a substituted or unsubstituted C2-C20 heteroaryloxy group, asubstituted or unsubstituted C3-C20 heteroarylalkyl group, a substitutedor unsubstituted C2-C20 heterocyclic group, and a halogen atom; and R₄is selected from hydrogen, a substituted or unsubstituted C1-C20 alkylgroup, and a substituted or unsubstituted C6-C20 aryl group.
 15. Thecomposite membrane of claim 14, wherein the at least one compoundrepresented by Formula 1 comprises isobutyltrimethoxysilane,octyltrimethoxysilane, propyltrimethoxysilane, decyltrimethoxysilane,dodecyltrimethoxysilane, octadecyltrimethoxysilane,3-methacryloxypropyltrimethoxysilane, n-octadecyltriethoxysilane,1H,1H,2H,2H-perfluorooctyltriethoxysilane, or(3-mercaptopropyl)trimethoxysilane.
 16. The composite membrane of claim14, wherein an amount of the condensation reaction product of the atleast one selected from compounds represented by Formula 1 is from about0.1 parts to about 30 parts by weight, based on 100 parts by weight ofthe plurality of gas blocking inorganic particles.
 17. A lithium airbattery comprising: an anode; a cathode; and the composite membrane ofclaim 1 between the anode and the cathode.
 18. The lithium air batteryof claim 17, wherein the plurality of aligned particles are positionedin a region of the composite membrane adjacent to the cathode.
 19. Abattery assembly comprising: an electrolyte; a lithium metal or alithium metal alloy; and the composite membrane of claim
 1. 20. Thebattery assembly of claim 19, wherein the electrolyte is a polymer solidelectrolyte.